含硫铝酸钙硅酸盐水泥中粉煤灰活化机理

用差示扫描-热重分析扫描电镜和化学分析法研究了含硫铝酸钙粉煤灰硅酸盐水泥和含硫铝酸钙矿渣硅酸盐水泥水化过程中水化产物的种类、形状、数量和孔溶液离子浓度等方面的变化规律.借助固体高分辨核磁共振波谱技术对水泥中硅氧四面体不同聚合状态的分布,Al的不同配位状态进行分析.结果表明:含硫铝酸钙硅酸盐水泥对粉煤灰激发作用大于对矿渣的激发作用,含硫铝酸钙粉煤灰水泥水化放热量多,促进粉煤灰玻璃体中AlO2-的溶出,在较高温度粉煤灰玻璃体网络结构激活,解聚速率加快.     

Improvement of the durability of glass fiber reinforced cement using blended cement matrix

Blended cements prepared with two fly ashes were used as matrices in glass fiber reinforced cement (GRC) composites in an attempt to improve their durability. The hydrated matrices from the two blended cements investigated here had similar strength and composition. Both fly ashes reduced the Ca(OH)₂ content to the same extent but in both cases the pH level was only slightly reduced compared to the portland cement matrix. In spite of these similarities, the GRC prepared with one fly ash showed considerable improvement in durability while the other one had only a small positive effect. SEM observations indicated that the improved durability in one case was associated with modification in the microstructure of the hydration products deposited in between the glass filaments, resulting in a much more open structure compared to that of portland cement matrix or the other blended cement. It is therefore suggested that the potential of the blended cement matrix to improve the durability of GRC is associated with its ability to modify the microstructure of the paste at the glass interface. This characteristic is not necessarily related to the overall composition of the blended cement matrix and to the reactivity of fly ash with Ca(OH)₂.     

高掺量混合材复合水泥的水化性能

通过水化微量热、化学结合水测定和X射线衍射、热重-差热分析、扫描电镜等测试方法研究了3种高掺量矿渣、粉煤灰、石灰石复合水泥的水化性能,并与硅酸盐水泥的水化进行了对比。结果表明：高掺混合材复合水泥的水化放热特征与硅酸盐水泥有明显不同,早期水化反应速度低于硅酸盐水泥,但后期由于矿渣、粉煤灰的二次水化反应使其水化速度增长较快。主要的水化产物亦为水化硅酸钙凝胶、钙钒石和Ca(OH)2晶体,但Ca(OH)2含量明显低于硅酸盐水泥浆体中的Ca(OH)2含量。     

Investigation of blended cement hydration by isothermal calorimetry and thermal analysis

Hydration of portland cement pastes containing three types of mineral additive; fly ash, ground-granulated slag, and silica fume was investigated using differential thermal analysis, thermogravimetric analysis (DTA/TGA) and isothermal calorimetry. It was shown that the chemically bound water obtained using DTA/TGA was proportional to heat of hydration and could be used as a measure of hydration. The weight loss due to Ca(OH)₂ decomposition of hydration products by DTA/TGA could be used to quantify the pozzolan reaction. A new method based on the composition of a hydrating cement was proposed and used to determine the degree of hydration of blended cements and the degree of pozzolan reaction. The results obtained suggested that the reactions of blended cements were slower than portland cement, and that silica fume reacted earlier than fly ash and slag.     

高掺量粉煤灰水泥胶凝材料的水化性能研究

用ＴＭＳ－ＧＣ,ＸＲＤ,ＤＴＡ,ＳＥＭ等方法研究了高掺量粉灰水泥胶凝材料的水化性能;分析了粉煤灰掺量、激发剂等对高掺量粉煤灰水泥胶凝材料水化性能的影响,并与硅酸盐水泥的水化性能进行了对比。结果认为：高掺量粉煤灰水泥的水化速度低于不掺灰的硅酸水泥的水化速度,但后期增长较快;激发剂能加快高掺量粉煤灰水泥的水化速度。     

Hydration of fly ash-portland cements

Hydration products of fly ash-portland cements were studied with x-ray diffraction (XRD), differential thermal analysis (DTA) and scanning electron microscopy (SEM) as part of a continuing research effort to understand the pozzolanic activity of fly ashes. It was found that the amount of calcium hydroxide crystals in the cement pastes is diminished due to the addition of fly ash to the cement. Ettringite was produced in the early age, and the consumption of sulfate by the formation of ettringite was accelerated by the addition of fly ash. A partial conversion of ettringite to monosulfate within the first 7 days of hydration in the fly ash-portland cement pastes, but the formation of ettringite continued to form up to at least 28 days of hydration in the pastes without fly ash. Examination of the fly ash bearing pastes showed, in all cases, varying amounts of calcium hydroxide and unreacted portland cement, with minor quartz and gehlenite hydrate. It appears that hydration reactions actually occur in the fly ash cement pastes more or less on a particle-by-particle basis.     

An improved basis for characterizing the suitability of fly ash as a cement replacement agent

Fly ash is a critical material for partial replacement of ordinary portland cement (OPC) in the binder fraction of a concrete mixture. However, significant compositional variability currently limits fly ash use. For example, the performance of OPC‐fly ash blends cannot be estimated a priori using current characterization standards (eg, ASTM C618). In this study, fly ashes spanning a wide compositional range are characterized in terms of glassy and crystalline phases using a combination of X‐ray fluorescence (XRF), X‐ray diffraction (XRD), and scanning electron microscopy with X‐ray energy‐dispersive spectroscopy (SEM‐EDS) techniques. The compositional data are distilled to a unitless parameter, the network ratio (N_r), which represents the network behavior of atoms that form alkali/alkaline earth‐aluminosilicate glasses that make up fly ashes. N_r is correlated with known composition‐dependent features, including the glass transition temperature and amorphous XRD peak (“hump”) position. Analysis of heat release data and compressive strengths are used to evaluate the impact of fly ash compositions on reaction kinetics and on the engineering properties of cement‐fly ash blends. It is shown that fly ashes hosting glasses with a high network ratio (ie, having a less stable glass structure) are more reactive than others.     

Analysis of mechanism on water-reducing effect of fine ground slag, high-calcium fly ash, and low-calcium fly ash

The addition of ultrafine powder (UFP) to concrete can improve the fluidity of concrete, showing a water-reducing effect. The aim of this article was to analyze the water-reducing mechanism of UFP both experimentally and theoretically. Three UFPs—fine ground slag, high-calcium fly ash, and low-calcium fly ash—were chosen for the study. The contrastive experiments were done to investigate the fluidity of mortars with 30%, 45%, 60%, and 75% equivalent cement replaced by fine ground slag, high-calcium fly ash, and low-calcium fly ash, respectively. The results showed the physical and chemical characteristic of the powders, such as their grain morphology, glass phase activities, densities, specific areas, and their grain cumulating conditions, can strongly affect their water-reducing effect.     

Effect of Fly Ashes with High Total Alkali Content on the Alkalinity of the Pore Solution of Hydrated Portland Cement Paste

The influence of two Spanish fly ashes (ASTM class F) with high total alkali content (equivalent to 2.0% and 2.6% Na₂O) on the alkalinity levels of the pore solutions expressed from hydrated portland cement pastes was studied during a period of 90 days from mixing. Mixtures with 0%, 15%, and 35% replacement of cement by fly ash were prepared with a water/mixture ratio of 0. 4. The effect of the fly ash on the pore solution depended mainly on the age and fineness of the fly ash.     

Activation of fly ash cementitious systems in the presence of quicklime: Part I. Compressive strength and pozzolanic reaction rate

In the first part of this study, the effect of industrially produced quicklime on the strength development and pozzolanic reaction rates of different fly ash/cement (FC) systems was investigated. Two high calcium fly ashes, diversified on their active silica and calcium oxide contents, and one with moderate calcium content were used. Strength development, hydration evolution, and pozzolanic reaction rates of the quicklime-fly ash-cement (QFC) systems were monitored and presented. Moreover, new efficiency factors were calculated for the activated systems in an attempt to optimize the quicklime addition in each case, whilst correlations were attempted between the nonevaporable water contents (W_n) and the cementitious efficiency factor (k values) of the activated systems. The addition of quicklime increased both the early and later strengths of the high-calcium fly ash specimens. For the two high-lime ashes tested, a 3% addition of quicklime was found to be the optimum dosage both for short and longer curing periods. It is possible that such an offer of lime fully employed the available silica from the ashes to form additional cementitious compounds, principally pozzolanic C-S-H. In the case of lower-lime fly ash, a small quantity of added lime (5%) was found to be effective only during the initial stages of the hardening process. When quicklime additions increased, no accelerating effect was detected, as a result of the diminished proportion of soluble silica in the pore solution. Identification of the generated hydration products, porosity of the activated mixtures and examination of their microstructure will be presented in Part II of the study.     

Studies of sintering of coal ash relevant to pulverized coal utility boilers: 1. Examination of the Raask shrinkage—electrical resistance method

The Raask shrinkage and electrical resistance method for determining the onset of sintering of fly ash has been tested on a soda lime glass, coal ASTM ashes, fly ashes and pulverized synthetic mineral mixtures. Results with the glass confirmed those of Raask and showed that particle size distribution and bulk density affected the resistance values: the sinter point was indicated by a change in the characteristic temperature coefficient of resistance. The shrinkage and electrical sinter points were usually the same, but a high Na content lignite gave 850°C for shrinkage but 600°C for characteristic resistance change. Sinter points were 200°C less for fly ash than for ASTM ash. The fly ashes had a slight enrichment of alkalies and a decrease in Fe content compared to the total ash. Holding a compact at a temperature above the sinter point gave increased strength and shrinkage, but no decrease in electrical resistance, indicating that the decrease in resistance as temperature increased was due to the establishment of contact points between particles, with little effect of the continued growth of a contact neck. Addition of pulverized sodium silicate or iron silicate glasses to a synthetic ash also reduced the sinter points, as did alkali additions, whereas addition of pyrite did not. It was concluded that the method was a valuable tool, but sources of variability had to be determined and controlled.     

Activation of Pozzolanic Reaction of Hydrated Portland Cement Fly Ash Pastes in Sulfate Solution

The activation of the pozzolanic reaction of fly ash in portland cement paste immersed in sulfate solution has been studied. Mixtures of two Spanish fly ashes (ASTM class F) with 0%, 15%, and 35% replacement of portland cement by fly ash were immersed in Na₂SO₄ solution, of 2880 ppm SO₄²⁻ concentration, for a period of 90 days. The resistance of the different mixtures to the sulfate attack was evaluated using the Koch-Steinegger test. The results showed that all of the mixtures were sulfate resistant, despite the high Al₂O₃ content of the fly ash. The diffusion of SO₄²⁻ and Na⁺ ions through the pore solution activated the pozzolanic reactivity of the fly ashes, causing microstructural changes, which were characterized by X-ray diffraction (XRD), mercury intrusion porosimetry (MIP), and scanning electron microscopy (SEM). As a result, the flexural strength of the mixtures increased, principally for the fly ash of a lower particle size and 35% of addition.     

Curing requirements of silica fume and fly ash mortars

The curing requirements of silica fume and fly ash mortars were investigated in this study. Silica fume and fly ash mortar specimens were moist cured for periods of 0, 3, 7, 14 and 28 days. After each of the five periods, the moist curing was interrupted by oven-drying the specimens at a temperature of 110°C for 3 days. The specimens were later tested for compressive strength and absorptivity. In this study, it was also determined whether the losses in strength and impermeability of silica fume and fly ash mortars due to an interruption in curing could be regained by recuring. The test results clearly indicate that the curing requirement of silica fume mortar is less than that of plain cement mortar, while in the case of fly ash mortar it is hogher than that of plain cement mortar.     

水泥、粉煤灰及其硬化体中Cr(Ⅵ)溶出条件与其影响因素

分析了国内外现行的溶出试验方法,研究了不同溶出试验条件对水泥、粉煤灰及其硬化体中Cr(Ⅵ)溶出的影响,探讨了粉煤灰中可溶性Cr(Ⅵ)最大溶出量的测定方法.结果表明:静置时间、温度、液固比、颗粒细度、振荡频率及振荡容器尺寸对水泥和粉煤灰及其硬化体中Cr(Ⅵ)的溶出及测定都具有一定的影响,其中振荡时间和浸提液pH值的影响较为显著.粉煤灰中Cr(Ⅵ)的溶出是一个缓慢连续的过程,其可溶性Cr(Ⅵ)最大含量的测定以多级萃取溶出试验为宜.     

Fire resistance of fired clay bricks-fly ash composite cement pastes

This work aims to study the effect of substitution of fly ash for homra on the hydration properties of composite cement pastes. The composite cements are composed of constant proportion of OPC (80%) with variable amounts of fly ash and homra. The addition of fly ash accelerates the initial and final sitting time, whereas the free lime and combined water contents decrease with fly ash content. The fly ash acts as nucleation sites which may accelerate the rate of formation of hydration products which fill some of the pores of the cement pastes. The fire resistance of composite cement pastes was evaluated after firing at 250, 450, 600, 800 °C with rate of firing 5 °C/min with soaking time for 2 h. The physico-mechanical properties such as bulk density and compressive strength were determined at each firing temperature. Moreover, the phase composition, free lime and microstructure for some selected samples were investigated. It can be concluded that the pozzolanic cement with 20 wt% fly ash can be used as fire resisting cement.     

Strength and microscopic characteristics of alkali-activated fly ash-cement

The effects of different activator concentration, liquid/fly ash ratio, and curing temperature and time on the compressive strength of specimens prepared from low-calcium fly ash activated with sodium hydroxide without the use of Portland cement were investigated. SEM, XRD and mercury intrusion porosimetry (MIP) were used to observed the structural feature, reaction products, and porosity and pore-size distribution of the specimens from alkaliactivated fly ash, respectively. It was found that the degree of reactivity, as shown by the compressive strength, the activator concentration and the ratio of liquid/fly ash, and the curing temperature always result to be significative factors. The 7, 14, and 28-day compressive strengths of specimens prepared from alkali-activated fly ash by 5M NaOH solution at 50 °C are 152, 219, and 263 kgf/cm², while those from 6M solution are 184, 225, and 267 kgf/cm², respectively. In SEM observation, the fly ash activated by the 5M NaOH solution shows a more continuous matrix with solid and non porous due to subsequent gel restructuring by amorphous alkaline aluminosilicate produced from alkali-activated fly ash.     

低品位粉煤灰的改性及其对水泥浆体强度和自收缩的影响

采用石灰石粉对低品位粉煤灰进行煅烧改性,利用X射线衍射、扫描电镜和能谱分析等方法对改性粉煤灰的矿物组成和化学组成进行表征.同时测定了掺改性粉煤灰的水泥浆体的抗压强度和自收缩,并采用背散射扫描电镜和压汞测孔仪研究了掺改性粉煤灰水泥浆体的微观结构.结果表明,粉煤灰经煅烧改性生成了水硬性矿物β-C2S,水化可生成CSH凝胶,改善了等外粉煤灰颗粒与水泥基体的界面粘接,降低了复合水泥浆体的孔隙率和自收缩,提高了复合水泥浆体的强度.     

Study on high-strength composite portland cement with a larger amount of industrial wastes

It is one of important measures for the sustainable development of cement industry to utilize industrial wastes. High-strength composite portland cement with a large amount of granulated blast furnace slag (GBFS), fly ash and limestone was prepared by separate grinding method, optimizing gypsum and using activators. The total amounts of blending materials are between 45% and 65% and the strength grades of cements reach 525 or even 625 according to Chinese national standard for composite portland cement. Besides setting time and strength, the hydration heat, drying shrinkage and sulfate resistance were also determined.     

Effect of fly ash on the kinetics of Portland cement hydration at different curing temperatures

This paper describes the effect of fly ash on the hydration kinetics of cement in low water to binder (w/b) fly ash-cement at different curing temperatures. The modified shrinking-core model was used to quantify the kinetic coefficients of the various hydration processes. The results show that the effect of fly ash on the hydration kinetics of cement depends on fly ash replacement ratios and curing temperatures. It was found that, at 20 °C and 35 °C, the fly ash retards the hydration of cement in the early period and accelerates the hydration of cement in the later period. Higher the fly ash replacement ratios lead to stronger effects. However, at 50 °C, the fly ash retards the hydration of the cement at later ages when it is used at high replacement ratios. This is because the pozzolanic reaction of the large volumes of fly ash is strongly accelerated from early in the aging, impeding the hydration of the cement.     

Steam hydration-reactivation of FBC ashes for enhanced in situ desulphurization

Bed and fly ashes originating from industrial-scale fluidized bed combustors (FBCs) were steam hydrated to produce sorbents suitable for further in situ desulphurization. Samples of the hydrated ash were characterized by X-ray diffraction analysis, scanning electron microscopy and porosimetry. Bed ashes were hydrated in a pressure bomb for 30 and 60 min at 200 °C and 250 °C. Fly ash was hydrated in an electrically heated tubular reactor for 10 and 60 min at 200 °C and 300 °C. The results were interpreted by considering the hydration process and the related development of accessible porosity suitable for resulphation. The performance of the reactivated bed ash as sulphur sorbent improved with a decrease of both the hydration temperature and time. For reactivated fly ash, more favourable porosimetric features were observed at longer treatment times and lower hydration temperatures. Finally, it was shown that an ashing treatment (at 850 °C for 20 min) promoted a speeding up of the hydration process and an increase in the accessible porosity.